Plant treatment composition



Patented Dec. 22, 1942 UNITED STATE 2,305,593 rum'r TREATMENTcomrosrrron x George S. Avery,

or to The Dow Mich.,

No Drawing.

Jr., New London, Comm, assi Chemical Company, Ml a corporation ofMichigan Application December 26, 1940,

ndiand,

Serial No. 371,827

15 Claims.

This invention relates to plant treatment compositions and isparticularly concerned with mixtures having both plant growth controland insecticidal properties and adapted to be applied to the aerialportion of plants. The present application is a continuation-in-part ofco -pending applications Serial No. 104,542, filed October 7, 1936, andSerial No. 120,449, flledJanuary 13, 1937.

Compounds such as indyl-acetic acid, alphanaphthyl-acetic acid, andalpha-naphthyl-acetamid have been recognized as having an efiect uponcertain phases of plant growth and development and are widely employedas active constituents of orchard sprays designed to control abscissionlayer formation and subsequent fruit drop. Other uses for which thesecomonnection with pounds have been applied are in c and the thestimulation of fruit development artificial fertilization less fruits.These compounds have been indefinitely classified as "plant auxins orplant hormones along with all naturally-occurring and syntheticproducts, including ethylene and ammonia, which exert any stimulatingeffect whatever upon plant growth. The naphthyl and indyl aliphaticacids and acidamid derivatives, however, are not the equivalent of suchnaturally-occurring materials as auxin A, auxin B, and auxin-containingextracts of plant and animal material. An important point ofdifferentiation resides in the fact that such naturally-occurringmaterials are almost invariably mixtures comprising substantial amountsof growth-inhibiting substances so that the effect of such mixture uponthe plant may be detrimental rather than desirable. Furthermore, suchnaturally-occurring products are (1) expensive because ofthe involvedprocesses required for their separation, (2) relatively unstable toacids, alkalies, and light, and (3) of indefinite purity and auxincontent, so that their effectiveness in a given composition is notreadily ascertained or pre-. dicted.

I have discovered that when a synthetic auxin is mixed with an organicinsecticidal toxicant a composition is obtained which may beadvantageously incorporated into spray and dust materials for thetreatment of the aerial portion of plants. desirable properties of suchcompositions are not just the sum of the properties of theirconstituents but that new and unpredictable results are obtained withsprays and dusts embodying the new mixtures.

f flowers to produce seed It has further been found that the The term"synthetic auxin as herein employed refers to chemically pure organiccompounds, particularly acids andacidamids, capable of causing anenlargement of the plant cell, as distinguished from those substancesthat influence plant growth by supplying nutrient to the plant, Theclass of synthetic auxins includes indylacetic acid, indyl-propionicacid, indyl-butyric acid, alpha-naphthyl-acetic acid,alpha-naphthyl-propionic acid, phenyl-acetic acid, fiuoreneacetic acid,anthracene-acetic acid, the esters and salts of such acids,alpha-naphthyl-acetamid, alpha-naphthyl-propionamid, and indylacetamid,all of which are readily prepared according to known methods of organicsynthesis. The term does not include inorganic stimulants auxin A, auxinB, or substances such as ammonia and ethylene which have undesirablevolatility. Each of the compounds included within the class contains anindole, benzene, 'naphthalene, anthrac and is characterized by havingplant hormonelike properties.

The expression aerial portion of plants" as herein employed refers tothe stem, leaf, flower, and fruit of the plant. The expression iscomparable to the term shoot in distinction to root, except that whereshoot is most frequently employed to designate a sprout or tender greengrowth from a seed or bulb, it is the intent of the present expressionbranches, stems, leaves, trees as well.

In carrying out the invention an organic insecticidal toxicant is mixedwith a synthetic auxin to obtain the desired composition. This mixingmay be carried out in any'suitable manner. For example, the insecticidaltoxicant and synthetic auxin, both in chemically pure form, may be mixedor ground together to form a con centrate adapted to be incorporated instandard dust or spray compositions for application to plants. In thisembodiment of the invention, the proportions of, materials employed varywith the form and manner in which the diluted concentrate is to beemployed. When the concentrate is to be subsequently incorporated into aspray, the proportions of constituents in the concentrate are soadjusted that at the preferred concentration of the insecticidaltoxicant the synthetic auxin will be present in the diluted compositionat from 2 to 40 parts per million and preferably between 5 to 15 partsper million. When the concentrate is to be subsequently incorporatedinto a dust, the amount of synthetic flowers, and fruit of ene, orfluorene ring structure.

to include the trunk,

- have been found auxin employed is such as to provide from to 1000parts per million, and preferably from 50 to 250 parts per million inthe finished composition. The exact limits observed in each instance aredependent upon the tolerance of the plant to be treated.

In preparing concentrates as outlined above, the mixture of insecticidaltoxicant and synthetic auxin may be modified with any suitable carrier,wetting, dispersing, or emulsifying agent. For example, the two majoringredients may be ground or otherwise dispersed in or on a solidcarrier such as bentonite, diatomaceous earth, gypsum, talc, wood flour,volcanic ash, or any mixture of one or more of such finely-dividedinerts to obtain the concentrate in the form of a duct or powder.Similarly, a solvent for both of the ingredients such as glycerol,alcohol, acetone, acetone-alcohol, glycol, or suitable ester or ethercompound may be employed to obtain a concentrate solution. In furthermodiflcations the synthetic auxin and toxicant may be ground with wateror other non-solvent to form .a paste concentrate, or so.processed as toform an emulsion containing high concentrations of each ingredient.

In any of the foregoing situations, such wetting, dispersing, andemulsifying agents as sodium-lauryl sulfate, sodium and potassium saltsof sulfonated oils, salts of sulfonated phenols, salts of sulfonatedbenzene and naphthalene, soaps, alkanolamines, sulfite pulping waste,caseinates, glyceryl esters, long chain fatty acids, etc. may beemployed as expedient, provided only that such added ingredient not beso reactive with the synthetic auxin or insecticidal toxicant as tolimit the effectiveness of the composition.

The concentrates as prepared above are subsequently diluted withfinely-divided solids or suitable liquid carriers to obtain dusts,aqueous dispersions, or emulsions adapted to be employed for thetreatment of the aerial portion of growing plants substantially ashereinafter set forth.

In an alternate procedure the insecticidal toxicant may be dispersed ina dilute spray or dust composition comprising the preferred amount ofthe synthetic auxin. Similarly, the required amount of synthetic auxinmay be added to an insecticidal spray or dust comprising an organictoxicant to obtain compositions falling within the scope of the presentinvention.

Regardless of whether the ultimate plant treatment material is preparedby dilution of a concentrate or by addition of one or both of theprincipal ingredients to a previously prepared dilute composition, theresults obtained upon application of the mixture to plant and'insectlife are the same. It has been found that the synthetic auxin frequentlyserves as an activator for the organic insecticide toxicant, whereby agreater than additive kill of insect pests is obtained. In addition tothis result, the organic insecticidal toxicant cooperates with thesynthetic auxin to materially increase the effectiveness of the latterin controlling the formation of abscission layer, as for example, inpreventing fruit drop. The application of the organic insecticides aloneto fruit-laden trees does not prevent premature dropping but frequentlyaccelerates-the abscission of the fruit. In view of the diversecharacter of the organic toxicants which to cooperate with the syntheticauxins, no limiting explanation or theory is presented for the phenomenaas observed.

While the present invention is concerned with compositions, comprisingorganic insecticides broadly, preferred groups of toxicants are (1)those compounds containing at least one sixmembered conjugated ringstructure such as the nicotine and benzene rings, and (2) extracts ofpyrethrinand rotenone-containing plants.

The following examples illustrate the invention but are not to beconstrued as limiting the same.

Example 1 A pyrethrin solution was prepared by dissolving a standardpyrethrum extract in a light petroleum distillate having a boiling rangeof 345508 F. and a flash point of 137 F. The amount of pyrethrum extractemployed was such as to give a concentration of 50 milligrams ofpyrethrins for each milliliters of solution. This composition was testedaccording to the Peet-Grady method substantially as described in Soap 8,No. 4, 1932, and found to give a knockdown of 93.7 per cent in 10minutes and a kill of 28.1 per cent in 48 hours against three-day oldhouseflies. Sufiicient alpha-naphthyl-acetic acid was then added to aportion of the pyrethrin solution to give a concentration of 10 partsper million of the alpha-naphthyl acetic acid. This modified compositionwas similarly tested according to the Feet-Grady method and found togive a knockdown of 94.3 per cent in 10 minutes and a kill of 44.1 percent in 48 hours. In a control determination, the alpha-naphthylaceticacid alone dissolved in the petroleum distillate in the amount of 20parts per million gave 0.00 knockdown and 0.00 kill according to thePeet-Gra'dy method.

Example 2 In a similar manner 0.0125 gram of rotenone was dissolved in amixture of 12.5 milliliters of methylethyl ketone with 87.5 millilitersof petroleum oil. This composition was found to give a knockdown of 12.7per cent in 10 minutes and a kill of 3.0 per cent in 48 hours accordingto the Feet-Grady procedure. A portion of this solution was modifiedwith 10 parts per million of alpha-naphthyl-acetic acid and found togive a knockdown of 30.9 per cent in 10 minutes and a kill of 9.5 percent in 48 hours. 20 parts per million of alpha-.naphthyl-acetic acid inthe petroleum oil-methylethyl ketone mixture gave 0.00 knockdown and0.00 kill in a control determination.

Example 3 Example 4 Alpha-naphthyl-acetic acid and is sodium salt werecompounded with a number of organic insecticidal toxicants to formconcentrates later diluted with water and applied on McIntosh appletrees immediately prior to the normal harvesting time of the apples. Noinjury to foliage or fruit was observed with any of the compositionsemployed. In each instance the proportions employed were such that, whenthe concentrate was diluted to give the concentration of organicinsecticidal toxicant' usually employed in tree sprays, theconcentration of the synthetic auxin in the dilute spray material wasapproximately parts per million. Control determinations were made inwhich a spray comprising 10 parts per million of alpha-naphthyl-aceticacid alone was applied to the aerial portions of the trees. The numberof apples present on each sprayed tree was determined both beforespraying and daily for a period of 7 days after the spray applicationand the percent drop for each tree calculated. The average per centfruit drop shown by several trees sprayed with alpha-naphthyl-aceticacid alone was 3.24. Although none of the insecticidal toxicantsemployed had any effect upon fruit drop when used alone, the combinationof such toxicants with the synthetic auxin gave results which were verysuperior to 1 those obtained with alpha-naphthyl-acetic acid alone. Thefollowing compositions are representative of those employed.

Parts by weight Composition A:

Beta (4 tertiarybutyl phenoxy)- ethanol 50.00 Alpha-naphthyl-acetic acid0.44 Peanut oil 2.9.56

Wetting agent (condensation product of ethylene oxide and an organicacid marketed as Emulphor EL This composition was dispersed at the rateof 227 grams per gallons of water and applied to a tree bearing 1269apples. At the end of 7 days. a total of 17 apples had fallen from thetree for a percentage drop of 1.34. This was 41.5 per cent of the dropobtained when alphanaphthyl-acetic acid alone was employed.

Parts by weight Composition B:

Beta (2.4.6 trichloro phenoxy)- beta'-chloro-diethyl ether 10.00 Beta (4tertiarybutyl phenoxy)- ethanol 40.00 Derris resin (containing 25 percent rotenone) 5.00 Alpha naphthyl-acetic acid 0.44 Peanut oil 24.56Wetting agent (Emulphor EL) 20.00

This composition was applied at a dilution of 227 grams per 25 gallonsof water to a tree bearing 697 apples. At the end of '7 days, only 8apples had fallen from the tree to give a percentage drop of 1.06. Thisdrop represents but 32.6 per cent of that taking place on trees treatedwith alphanaphthyl acetic acid alone.

Parts by weight Composition C:

2.4-dinitro-6-cyclohexyl-phenol 11.25

Alpha-naphthyl-acetic acid 0.79 Sodium lauryl sulfate"--. 8.90 79.00

Gypsum Parts by weight Composition D:

2.4-dinitro-G-cyclohexyl-phenol 0.80 Sulfur 93.98 Inert (wetting anddispersing agent) 5.00 Alpha-naphthyl-acetic acid 0.22

Parts by weight Composition E:

Dicyclohexyl-amine salt of 2.4-dinitrofi-cyclohexybphenol 20.00Bentonite 10.00 Gypsum 67.41 Sodium lauryl sulfate 2.00Alpha-naphthyl-acetic acid 0.59

This dust concentrate was applied at the rate of grams per 25 gallons ofwater to a tree bearing 764 apples. After 7 days, 4 apples had fallenfrom the tree for a drop of 0.51 per cent. This drop is but 15.7 percent of that allowed {by alphanaphthyl-acetic acid alone.

Parts by weight Composition F:

2.4-dinitro-6-cyclohexyl-phenol 22.20 Triethanol amine 5.50Alpha-naphthyl-acetic acid 1.83 Water 70.45

6-cyclohexyl-pluenol 20.00 Bentonite 10.00 Gypsum 67.41 Sodium laurylsulfateu 2.00 Alpha-naphthyl-acetic acid 0.59

This concentrate was applied at the rate of 170 grams per 25 gallons ofwater to a tree bearing 7B7 apples. After 7 days,'l3 apples had fallenfrom the tree for a drop of 1.65 per cent. This drop is 51 per cent ofthat permitted by alphanaphthyl-acetic acid alone.

Composition H: Parts by weight Sodium 2.4-dinitro-phenate 36.55 Sodiumalpha-naphthyl-acetate 5.70 Sodium lauryl sulfate 57.75

This composition was applied at the rate of 19.5 grams per 25 gallons ofwater to a tree bearing 951 apples. At the end of 7 days, 14 apples hadfallen from the tree to give a drop of 1.47 per cent. This representsonly 45.5 per cent of the drop resulting when alpha-naphthyl-acetic acidalone was employed.

Composition 1: Parts by weight Phenothioxin 20.00 Gypsum 67.82 Bentonite10.00 Alpha naphthyl-acetic acid 0.18 Sodium lauryl sulfate 2.00

.lons of water.

This composition was applied at the rate of 568 grams in 25 gallons ofwater to a tree bearing 1214 apples. At the end of 7 days, 12 apples hadfallen from the tree for a drop of 0.99. per cent. This represents 30.5per cent of the fall observed when alpha-naphthyl-acetic acid alone wasemployed.

Composition J Parts by weight Phenothioxin 5.00 Beta-(4 tertiarybutylphenoxy) -ethanol 20.00 Alpha-naphthyl-acetic acid 0.18 Derris resin2.00 Acme white oil 52.82 Wetting agent (Emulphor EL") 20.00

This concentrate was applied at the rate of 568 grams per 25 gallons ofwater to a tree bearing 1641 apples. At the end of 7 days. 28 apples hadfallen from the tree for a drop of 1.71 per cent. This is 52.5 per centof the drop observed when alpha-naphthyl-acetic acid was employed alone.

Composition K: Parts by weight Phenothioxin-lO-oxide 20.00 Gypsum} 67.82Bentonite 10.00 Alpha-naphthyl-acetic acid 0.18 Sodium lauryl sulfate2.00

This composition was applied at the rate of 568 grams per 25 gallons ofwater to a tree bearing 571 apples. At the end of 7 days, 6 apples hadfallen from the tree for a drop of 1.05 per cent. This represents 32.5per cent of the drop observed with alpha-naphthyl-acetic acid alone.

Composition L: Parts by weight Phenothiazine 20.00 Alpha-naphthyl-aceticacid 0.18 Gypsum 67.82 Bentonite 10.00 Sodium lauryl sulfate 2.00

This composition was applied at the rate of 568 grams per 25 gallons ofwater to a tree bearing 855 apples. At th end of 7 days, 13 apples hadfallen for a drop of 1.52 per cent. This represents 47 per cent of thedrop obtained with a spray solution comprising alpha-naphthyl-aceticacid alone.

Composition M: Parts by weight Pineyl-diphenyl oxide 80.00 Sulfonatedsperm oil (sold as NOPCO 1216") 19.82 Alpha-naphthyl-acetic acid 0.18

This concentrat was added to water in the amount of 568 grams per 25gallons and sprayed on atree bearing 960 apples. At the end of 7 days,15 apples had fallen for a drop of 1.58 per This represents 48 per centof the drop observed when alpha-naphthyl-acetic acid was employed alone.

had fallen from the tree to give a Composition 0: Parts by weight Gamma-(2-cyclohexyl phenoxy) -propyi thiocyanate 22.50 Pine oil 48.06Sulphonated sperm oil (NOPCO 1216") 23.00 Acme white oil 6.00Alpha-naphthyl-acetic acid 0.44

This composition was applied at the rate of 227 grams per 25 gallons ofwater to a tree bearing 526 apples. At the end of 7 days, 6 apples hadfallen for a drop of 1.14 per cent. This repre sents 35.2 per cent ofthe fall observed when alpha-naphthyl-acetic acid was employed alone.Composition P: Parts by weight Nicotine sulfate (as alkaloid) 20.50Sodium alpha-naphthyl-acetate 0.35 Sodium laury1 sulfate 3.62 Water75.53

This concentrate was applied 708 apples at the rate of 312 grams per 25gallons of water. At the end of 7 days, 7 apples had fallen from thetree for a drop of 0.99 per cent. This represents 30.5 per cent of thedrop obtained with alpha-naphthyl-acetic acid alone.

Composition Q: Parts by weight Ethylene glycol diacetate 99.26Alpha-naphthyl-acetic acid 0.74

This composition was applied to 1044 apples at the rate of 4 fluidgallons of water. At the end of 7 a tree bearing ounces per 25 days, 12apples drop of 1.15 per cent. This is 35.5 per cent of the drop observedwhen alpha-naphthyl-acetic acid alone was applied.

Other compositions which may be similarly employed include thefollowing:

Composition R: Parts by weight Beta -(2.4.6-trichloro-phenoxy)betathiocyano-diethyl ether 22.50 Alpha-naphthyl-acetamid 0.44 Pine oil48.06 Sulfonated sperm oil (NOPCO 1216") 23.00

Acme white oil 6.00

This composition may be applied to growing trees at a dilution of 227grams per 25 gallons of water.

Composition S: Parts by weight Trichloro-monofluoro-benzene 20.00Bentonite 77.82 Alpha-naphthyl-acetic acid 0.18 Sodium lauryl sulfate2.00

This composition 568 grams per 25 may be applied at the rate of gallonsof water.

Composition T: Parts by weight xanthone -s 97.67Sodium-alpha-naphthyl-acetate 0.33 Sodium lauryl sulfate 2.00

This composition may be employed at the rate of 342 grams in 25 gallonsof water.

Composition U: Parts by weight Dibutyl phthalate" 50.00 Derris resin10.00 Indyl-acetic acid 0.44 Peanut oil 19.56

Wetting agent (Emulphor EL) 20.00

This composition may be applied at the rate of 227 grams per 25 gallonsof water.

In a similar manner such compounds as indylbutyric acid, indyl-propionicacid, alpha-naphto a tree bearing thyl-propionic acid, phenyl-aceticacid, fluorene-acetic acid, alpha-naphthyl-propionamid, andindyl-acetamid as well as the organic and inorganic salts of theforegoing acids may be compounded with organic insecticides to obtaincompositions having the same general properties as those shown in theforegoing examples.

Other modes of applying the principle of my invention may be employedinstead of those explained, change being made as regards the materialsemployed, provided the products described in the following claims bethereby obtained.

I therefore particularly point out and distinctly claim as my invention:

1. A plant treatment composition comprising a synthetic auxin and anorganic insecticidal toxicant.

2. A composition of matter adapted to be applied to the aerial portionof plants comprising an organic insecticidal toxicant and a relativelysmall amount of a synthetic auxin.

3. An insecticidal and plant growth control concentrate adapted to bediluted to produce compositions for application to the aerial portion ofplants comprising an intimate mixture of an organic insecticidaltoxicant and a synthetic auxin.

4. A spray composition adapted to be applied to the aerial portion ofplants comprising an organic insecticidal toxicant and from 2 to 40parts per million of a synthetic plant auxin.

5. A dust composition adapted to be applied to the aerial portion ofplants comprising an organic insecticidal toxicant and from to 1000parts per million of a synthetic auxin.

6. An insecticidal and plant growth control concentrate adapted to bediluted to produce compositions for application to the aerial portion ofplants comprising an intimate mixture of an organic insecticidaltoxicant, a synthetic auxin, and a wetting agent.

7. A plant treatment composition comprising alpha-naphthyl-acetic acidand'an organic insecticidal toxicant. v

8. A composition of matter adapted to be applied to the aerial portionof plants comprising an organic insecticidal toxicant and a relativelysmall amount of alpha-naphthyl acetic acid.

9. An insecticidal and plant growth control concentrate adapted to bediluted to produce compositions for application to the aerial portion ofplants comprising an intimate mixture of an organic insecticidaltoxicant and alpha-naphthyl-acetic acid.

10. A spray composition adapted to be applied to the aerial portion ofplants comprising an organic insecticidal toxicant and from 2 to 20parts per million of alpha-naphthyl-acetic acid.

11. An insecticidal and plant growth control concentrate adapted to bediluted to produce compositions for application to the aerial portion ofplants comprising an intimate mixture of an organic insecticidaltoxicant, alpha-naphthyl-acetic acid, and a wetting agent.

12. A composition of matter adapted to be applied to the aerial portionof plazflzs comprising an organic insecticidal toxicant and a relativelysmall amount of the sodium salt of alpha-naphthyl-acetic acid.

13. A spray composition adapted to be applied to the aerial portion ofplants comprising an organic insecticidal toxicant and from 2 to 40parts per million of the sodium salt of alpha-naphthylacetic acid.

14. A composition of matter adapted to be applied to the aerial portionof plants comprising an organic insecticidal toxicant and a relativelysmall amount of indyl-acetic acid.

15. A spray composition adapted to be applied to the aerial portion ofplants comprising an organic insecticidal toxicant and from 2 to 40parts per million of indyl-acetic acid.

GEORGE E. AVERY, JR.

CERTIFICATE OF CORRECTION. Patent No. 2,50 ,593. December 22, 19!;2.

GEORGE s. AVERY, JR.

It is hereby certified that error appears in the printed specificationof the above numbered patent reqhiring' correction as follows Page 2,iirat. column, 1ine'l7 for "'duct" read --duat--; page 5, secondcolumn,- line 14.5, for Glycerine' read --G1ycine--; and that the acidLetters Patent should be read with this ccrrection therein that the samemay cmfom to the record of the case in the Patent Office.

Signed and sealed this 16th day of March, A, D. 1911.5;

( Henry Van Arsdale,

Acting Commissioner of Patents.

